RI 5782 Oxidation Of Anthracite With Concentrated Nitric Acid ? Summary

In this study by the Federal Bureau of Mines Pennsylvania anthracite from the Eastern Middle field was oxidized by concentrated nitric acid at steam-bath temperature for 24 to 1,000 hours. The quantitative data obtained include yields of nitric-acid soluble and insoluble products and the distribution of carbon and ash in each. The acid-insoluble residues were examined for solubility in aqueous sodium hydroxide. With a sodium hydroxide concentration of at least 1 normal, a portion of the residue could be extracted in the form of a true solution. With lower alkali concentrations, peptization occurred. Alkali solubility of the residue increased with length of oxidation. However, when expressed in percentages of original coal weight, the alkali solubility remained essentially constant after 192 hours of oxidation. This suggests that the alkali-soluble products are converted to acid-soluble products at the same rate as the original coal substance is converted to alkali-soluble material. Microscopic observations of the peptization of the acid-insoluble residues revealed a gross micellar physical structure. The action of nitric acid is apparently not restricted to the surface of a coal particle. The acid penetrates the particle through the pore structure, dissolving some of the ash and altering the bonds between the coal micelles. The bond alteration, as indicated by ultimate analyses, involves the physical and chemical adsorption of the components of nitric acid. Some of the altered bonds are not thermally stable; this instability is shown by the complete loss of peptizing ability when the acid-insoluble products are heated above 200° C. This loss is accompanied by the evolution of water, oxides of nitrogen, and hydrocyanic acid.